Transcriptive material for making copies without use of carbon paper



United States Patent Int. Cl. B41c 1/06; 344d 1/14 U.S. Cl. 11736.4 24 Claims ABSTRACT OF THE DISCLOSURE Transcriptive materials and the process for producing such materials are provided. According to the process a flexible sheet carrier is coated with a mixture of a colored pigment and a high-molecular weight binding agent; the color layer is dried to a hardness such that it does not give ofi? color transferable directly to a writing sheet placed thereunder when the carrier of the color layer is written upon with pressure on its uncoated surface; there is then applied to the dried color layer an aqueous dispersion containing as essential dispersed matter 4.5 to 14% by weight of aliphatic saturated polycarboxylic acid of a molecular weight ranging from 1,000 to 20,000 and an acid number in the range of to 150, which acid comprises a main chain of carbon atoms, the terminal groups of which are free from carboxylic groups, and the carboxyl groups are bonded to the main chain as branches; the top layer is then dried at a temperature below the fusion point of the said carboxylic acid.

This application is a continuation application of application Ser. No. 395,589 filed Sept. 14, 1964 and abandoned since the filing of the present application.

This invention relates to transcriptive materials for making copies without the use of carbon paper; and to process for manufacturing such materials.

Many types of transcriptive material are known which serve, when written upon, to make simultaneously one or several copies without the use of carbon paper. A conventional transcriptive material consists, for example, of a flexible sheet such as a paper sheet, as carrier, which bears on one side thereof a color layer for transmitting to a copy sheet the writing which is being applied to the color-free side of the carrier. The color layer may be of varying composition and comprise, e.g., pigment as well as binders and/or fillers.

The carrier, to which the writing to be transcribed, is applied under pressure, for instance, by means of a writing device such as the letters of a type-writer, may consist of common writing paper, type-writer paper, or like writing material.

Transcriptive sheet materials which permit the making of copies without use of carbon paper have been known in the art under such names as manifolding sheet, copying paper, transfer sheet, transcript material and others.

While numerous proposals are known for the preparation of the color layer on such write-through sheet material, it remains a difiicult problem to produce a transcriptive material which satisfies the various practical requirements made on such materials, namely clean handling, i.e. freedom from smearing, and obtainment of a suflficient number of well-readable copies of sharply-delineated contours, with use of a writing pressure of average strength.

These requirements are met in a satisfactory manner 3,468,692 Patented Sept. 23, 1969 "ice by the transcriptive material according to the invention which comprises the essential constituents subsequently described:

A flexible sheet carrier one surface of which is adapted for being written upon with a writing tool exerting a pressure thereupon, which pressure is of a magnitude as is generated when writing by hand with a ball-pen or pencil, lor by a manual or electric typewriter.

Flexible sheet carriers suitable for use in the transcriptive material according to the invention are sheets of paper, woven or non-woven fibrous materials of cellulosic or other material, foils and films of synthetic polymeric resin or the like materials, but also other sheets of organic or inorganic substances of such surface texture that the color layer can satisfactorily adhere thereto.

At least a portion of one surface of said sheet carrier bears a color layer consisting essentially of a mixture of a colored pigment and a high-molecular-weight organic binding agent which is free from waxy, oily and fatty components, in particular, polyvinylacetate, which layer is of such hardness and fastness to rubbing that no pigment rubs off or migrates therefrom directly into cellulosic material of a writing sheet placed thereunder when the carrier is subjected to the normal pressure exercized by writing on its uncoated surface.

Colored pigments suitable for preparing the color layer of the inventive transcriptt materials are e.g. the following dyestuffs denominated in accordance with the Colour Index 2. Edition, 1956: CI. Pigment Black 11, Cl. Pigment Blue 15 or 29, Cl. Vat Blue 1 or 14 (as pigments), C.I. Pigment Green 15, C.I. Pigment Orange 2 or 19 or 20, CI. Pigment Red 3 or 48 or 49 or 54 or 63, CI. Pigment Violet 4 or 5, CI. Vat Violet 1 (as pigment), CI. Pigment Yellow 1 or 23 or 31 or 34, Cl. No. 16185 in the form of Amaranth Maroon Lake.

Covering said color layer without penetrating into the some is a top layer which consists essentially of a deposit obtained from an aqueous dispersion of 4.5 to 14% by weight of aliphatic saturated polycarboxylic acid of a medium molecular weight ranging from 1,000 to 20,000 and an acid number of 10 to 150, which acid comprises a main chain of carbon atoms the terminal groups of which are preferably free from carboxyl groups, and the carboxyl groups are bonded directly to said main chain as branches or to aliphatic side chains of, preferably from 1 to 4 carbon atoms which are in turn linked to the said main chain of carbon atoms.

In carrying out the invention in practice, the saturated aliphatic polycarboxylic acids have, within the limits defined hereinbefore, for example, medium molecular weights of from 1,000 to 4,000 in the case of acid members ranging from 100 to 150, or medium molecular weights of 15,000 to 20,000 in the case of acid numbers of 10 to 30, 1

The carboxyl groups of these polycarboxylic acids used in the preparation of the top layer of the transcriptive material according to the invention may be bonded directly to the main carbon chain of the polymeric acid substance; or they may be present therein as substituents of short aliphatic, preferably alkyl side chains, preferably of the above-defined number of carbon atoms, which are in turns linked to the aforesaid rnain carbon chains; such side chains are preferablyCH COOH or --CH CH --COOH groups.

Particularly satisfactory results are obtained with transcriptive sheet materials according to the invention, the top layer of which is prepared using aliphatic saturated polycarboxylic acids in which a portion of the carboxylic acid radicals has been esterfied to such a degree that the polymers possess saponification numbers in the range of from 30 to and acid numbers of from 10 to 140, i.e., the polycarboxylic acids contain simultaneously esterified and free carboxylic acid radicals. Esterification of the carboxylic acid groups can range from 1% up to 80% of the total of carboxylic acid radicals present and can be carried out with aliphatic alcohols, preferably with alkanols of from 1 to 20 carbon atoms, as alcoholic ester component. Particularly preferred are the products obtained by esterification of the carboxylic acid groups, within the above-defined percentage limits, with aliphatic poly-ether alcohols, especially with poly-alkoxyalkanols or hydroxy-poly-alkoxy-alkanols, having a total of from 2 to 21 carbon atoms and from 1 to 10 oxygen atoms, the esterified groups in the latter case containing terminal hydroxy groups.

High-molecular-weight polycarboxylic acids of the above described special structure are of excellent dispersibility and especially good adherence to cellulose and to cellulosic writing materials. The esterified products are produced in a manner known per se, by esterification with methanol, ethanol, propanol, isopropanol, butanol, isobutanol, ethylene glycol, glycerol, propylene glycol, mannital, pentaerythritol and the like or by reaction of free carboxylic acid groups of the polymer or starting materials therefor with ethylene oxide or propylene oxide.

An advantageous embodiment of the invention, comprises a top layer of the novel transcriptive material in which the carboxyl groups of the saturated aliphatic polycarboxylic acids of a medium molecular weight of 1,000 to 20,000 have been esterified with a mixture of monoaud/or polyhydric alkanols, whereby the saponification number of the polymeric product ranges from 30 to 70 and the acid number from 10 to 150.

The abovexlescribed polycarboxylic acids are produced in a well-known manner, for instance, by oxidation of branched polyethylenes or polypropylenes or by copolymerization of mixtures of ethylene and propylene, with unsaturated monoor di-carboxylic acids.

Substances of such a kind suitable for preparing the top layer of the incentive transcriptive material are e.g. OA-Wachs LK 5012 and Emulsion LK 5022 produced by the Badische Anilinu. Soda- Fabrik A.G., Ludwigshafen, A-C Polyethylene 629 produced by the Allied Chemical Corporation, New York, and the special types E10, E13, E14, HDE and LVE 01f Epolene--waxes produced by the Eastman Chemical Products, Inc., Kingsport, Tenn.

The above-described polymeric products have several advantageous properties; they are particularly suited for the formation of aqueous dispersions, in which form they are used in the preparation of the top layer of the novel transcriptive material, which top layer imparts the transcriptive property to the said material. It is a further advantage of the said polymeric products that they are produced in the form of aqueous polymeric dispersions which can directly form such top layer.

In order to form the above-mentioned top layer, the polymeric carboxylic acids described hereinbefore can also be used in mixture with high-molecular-weight substances which also contain polar groups in their molecules; carboxylic acid groups, carboxylic acid amide, carboxylic acid ester and polyether groups have been found to be especially advantageous polar groups.

Thus, the following mixtures are suitable for use in the formation of the top layer according to the invention: Above described polycarboxylic acids mixed with vinyl polymerizates containing polar groups or Wi-h co-polymerizates of vinyl chloride, acrylic acid and, optionally, vinyl esters or with other co-polymerizates which have been produced using unsaturated carboxylic acids or with polyacrylic acid esters or amides which can still contain free or salt-form carboxyl groups or with derivatives of polymethacrylic acid or with montan wax containing carboxyl groups or ester groups or with several such components.

As polymeric substances of such a kind containing polar groups and suitable to be mixed with the polycarboxylic 4 acids according to the invention may be used e.g. the special types D, 200D, 300D, "-1250D, 1300B, 1400B, 1450B of Lutofan or the special types 1D, 4D, 14D, 40D, 300D, 350D, 400D, 450D, 500D, 550D, 6001) of Acronal, both type groups produced by the Badische Anilinu. Soda-Fabrik A.G., Ludwigshafen, and KP Wachs or KSE-Wachs, both produced by the Farb- Werke Hoechst A.G., Frankfurt-Hoechst.

The polycarboxylic acids which form the essential constituents of the above described top layer, e.g. polyethylene and polypropylene derivatives, are preferably present in such mixtures as the major portion thereof, in amounts of at least 60% by weight of the mixture.

Advantageously, the high-molecular polycarboxylic acids can be used in mixture with esters of polyacrylic acid and alkanols having 1 to 10 carbon atoms, in the form of aqueous dispersions.

Preferably the color pigment layer is of a thickness corresponding to 2 to 4 grams per square meter of carrier surface, while the top layer of polycarboxylic acid is preferably of a thickness of 0.5 to 3 grams per square meter of carrier surface.

The transcriptive material according to the invention permits production of Well-readable manual or typed transcripts on common, untreated writing or printing papers. The copy of the writing thus produced on the latter type of paper has a dry, non-Waxy touch and does not rub off or smear.

The above-described transcriptive material according to the invention is excellently suited for the production of text copies on a high number of superimposed sheets, the backs of which are provided with the above-described color layer and top layer according to the invention. A set of such papers can, for instance, be fastened together in pad-form.

It is also possible to provide endless rolls or strips of such sets of sheets each bearing the color layer and top layer according to the invention, or a set may be formed by zig-zag folding of a long web of such sheet material.

The above-described novel transcript paper is produced by the process according to the invention which comprises:

(a) Coating at least a portion of one surface, or one entire surface, of a flexible sheet carrier with the above described pigment-binding agent mixture by applying the mixture in a conventional volatile solvent; and

(b) Drying the resulting color layer to such hardness that it does not give off color transferable directly to a writing sheet placed thereunder when the carrier of the color layer is written upon with pressure on its uncoated surface; and

(0) Applying to the dried color layer an aqueous dispersion containing as the essential dispersed matter the above described polycarboxylic acid; and

(d) Drying the top layer formed by said dispersion at a temperature below the fusion point of said saturated aliphatic polycarboxylic acid, which top layer adheres firmly to said color layer Without penetrating through the same.

The application of the aliphatic polycarboxylic acid or a mixture of such acid with the other substances described hereinbefore, in the form of aqueous dispersions offers great advantages over the use of organic solvents, e.g. chlorinated hydrocarbons which have hitherto been used to apply top coatings of this kind. Handling of the aqueous dispersions is safer and healthier than that of the conventional organic solutions. Moreover the preparation and use of these aqueous dispersions is much more economical.

However, it is also possible to apply the polycarboxylic acids or the above-described mixtures containing the same optionally in the form of solutions in organic solvents or as a melt.

More in detail, the manufacture of the transcriptive material according to the invention is carried out by first applying to a carrier of the type described, a solution or dispersion of the pigment dyes and the above-defined binding agent, e.g. polyvinyl acetate. Well-known application techniques such as application with a brush or a roller, pouring, printing, or draw-down with a doctor blade or: air-knife can be employed. The color layer is thus formed on the carrier preferably in a thickness of 2 to 4 grams per square meter and dried in a hot air current. The pigment layer is then coated with the top layer by applying thereto the aqueous dispersion of the abovedescribed saturated aliphatic polycarboxylic acids with or without an admixture of other high-molecular-weight organic materials containing polar groups as defined hereinbefore, in such amounts that after drying there remains a thin layer, not exceeding 3 grams per square meter of the surface of the pigment layer; conventional application techniques using measuring and metering apparatus are employed. Thus, application can be carried out by means of rollers with the aid of doctor blades adjusted to meter the amount of top layer-forming dispersion applied, or by means of rotary printing, immersion, application with a brush, pouring on or spraying on of the said dispersion, or in a similar known manner.

The top layer is then dried in a hot air current having a temperature of 45 to 55 C. As a result of substantially exceeding this upper temperature limit the polymeric particles of the dispersion might melt and coalesce, which is to be avoided, since the color-transfer power of the top layer would suffer. Moreover, drying of the top layer must be effected immediately and rapidly in order to prevent undue penetration of the top layer constituents into the color layer below the same. Drying with infrared radiation is more rapid than with a hot air current. On the other hand there is danger of overheating the top layer. It is generally preferred to move a web of the carrier, e.g. a paper web, on which the color pigment layer has been formed and on which a coating of aqueous top layer-forming dispersion has been applied, immediately thereafter into a drying chamber or zone in which the air current of 45 to 55 C. or a corresponding infrared irradiation is applied. In order to avoid the above-mentioned drawbacks, the web should be passed through the hot air-drying chamber at a speed of 50 to 70, preferably about 60 meters per minute, or through an infrared irradiation zone more rapidly, e.g. at 80 to 120, and preferably at about 100 meters per minute.

A typical transcript sheet produced by the method according to the invention bears a color layer of a thickness of 4 to 6 microns and a top layer of 2 to 4 microns. The invention is further illustrated by the following nonlimitative examples in which all temperatures are given in degrees centigrade and all parts and percentages are by weight unless expressly stated ottherwise.

Example 1 (a) A mixture serving for the production of a color layer is produced by mixing the following components together and grinding them in a ball mill:

15 parts by weight of the alizarin-alurninum lake described by Venkataraman in The Chemistry of Synthetic Dyes, vol. II (1952), pages 820-821, 0.8 part of silica, 4.8 parts of polyvinyl acetate dissolved in 9.4 parts of ethyl acetate and 70.0 parts of ethanol.

The resulting dispersion is then applied by a printing roller onto a web of cellulose paper in an amount of 40 grams per square meter of the web, excess is removed and the layer is then dried at 50 C., so as to leave a color layer of 2 grams per square meter on the paper web. The thickness of this color layer is about 0.005 mm.

The resulting paper coated with the color layer is not yet suited for writing through to obtain copies on other paper sheets.

(b) For this purpose, the following mixture is produced:

20 parts of an aqueous dispersion containing 40% of OA-Wachs LK 5012 produced by the Badische Anilinu. Soda- Fabrik A.G., Ludwigshafen, i.e. a polycarboxylic acid containing esterified and free carboxylic acid groups in amounts corresponding to a saponification number of 50-60 and an acid number of 25-30 respectively, and a viscosity, at melting, of 530-550 centistokes and a solidification point of 96 C., 5% of triethanolamine oleate as emulsifying agent and 2% of galactomannan thickener and 3% Lutonal M40 (polyvinyl methyl ether) as dispersion stabilizer, the balance consisting of water, are mixed intimately with parts of water.

The resulting dispersion is applied with a roller onto the color layer of the paper web, produced as described above under (a) and the web is moved immediately at a speed of about 60 meters per minute through a drying chamber in which it is dried in a stream of hot air having a temperature of 50-55.

The resulting transcriptive paper web is cut into sheets and is now ready for use. By placing it with its coated side on an untreated sheet of writing paper and writing on the uncoated side of the transcriptive paper, with normal pressure, a sharply delineated copy of the written text is produced on the untreated writing paper. The copy text does not smear and is very resistance to rubbing. It does not stain the fingers of a person handling the copy, as is the case frequently with copies prepared with known transcriptive paper.

Similar results are obtained when repeating the above example, but using instead of a cellulosic paper web an endless strip of cellulose acetate foil.

Example 2 (a) 15 parts of the alizarine-aluminum lake used in Example 1, and 4.0 parts of silica are intimately mixed with 2.5 parts of ethyl cellulose dissolved in 78.5 parts of ethanol, the whole is ground in a 'ball mill to produce a fine dispersion.

The mixture is then applied to one side of a cellulose paper web and dried in the same manner as described in Example 1.

(h) Then, 16 parts of the same aqueous dispersion of polycarboxylic acid as used in the preceding example is mixed with 8 parts of an aqueous dispersion consisting of about 50% of vinylchloride-acrylic acid copolymer of a pH value of 5-6 having free carboxyl groups (commercially available as Lutofan 200D) and the balance of water, and with 76 parts of water, and the resulting mixture is then applied in the same manner and in the same amount onto the color layer formed according to step (a) of this example, as is described under step (b) of Example 1.

A good transcriptive paper similar to that of Example 1 is obtained.

Example 3 (a) A color layer is produced on a web of writing paper by the procedure and with the mixture described in step (a) of Example 1.

(b) 16 parts of an aqueous dispersion of polycarboxylic acid as used in Example 1, 8 parts of a copolmerisate of different polyacrylic acid esters (commercially available as Acronal 500D) and 76 parts of water are mixed, and the resulting dispersion is used as described in Example 1 for the production of a top layer on the color layer obtained in step (a) of this example.

The resulting transcriptive paper possesses good qualities similar to those of the paper produced in Example 1.

Example 4 (a) A color layer is produced on a web of writing paper by the same procedure and with the same mixture as described in step (a) of Example 1.

(b) 35 parts by weight of an aqueous dispersion of polyoarboxylic acid as used in Example 1. 44 parts of an aqueous dispersion containing about 10% of montan wax ester (commercially available as KPE wax), 2.5 parts of an aqueous dispersion containing about 50% of vinylchloride-acrylic acid copolymerizate (commercially available as Lutofan 200 D), 2.5 parts of an aqueous dispersion containing about 50% of a co-polymerizate of different acrylic acid ester (commercially available as Acronal 500 D), and 16 parts of water are mixed intimately with each other, and the resulting dispersion is used as described in Example 1 for the production of a top layer on the color layer obtained in step (a) of this example.

The resulting transcriptive paper possesses good qualities similar to those of the paper produced in Example 1.

Example 5 (a) A color layer is produced on a web of writing paper by the same procedure and with the same mixture as described in step (a) of Example 1.

(b) 25 parts by weight of Emulsion LK 5022 produced by the Badische Anilinu. Soda- Fabrik A.G., Ludwigshafen, i.e. an aqueous dispersion containing 40% of a polycarboxylic acid having an acid number of 20-30, a saponification number of 5 0-60 and a molecular weight of 20,000 and the same content of emulsifier and dispersion-stabilizer as in the dispersion of Example 1, and 75 parts of water are mixed with each other and then applied in the same manner and in the same amount onto the color layer formed according to step (a) of this example, as is described under step (b) of Example 1.

A good transcriptive paper similar to that of Example 1 is obtained.

Example 6 (a) A color layer is produced on a web of writing paper by the same procedure and with the same mixture as described in step (a) of Example 1.

(b) 30 parts by weight of the same aqueous dispersion as used in Example 5, 44 parts by weight of the montan Wax ester dispersion as used in Example 4, 2.5 parts of the vinyl chloride-acrylic acid copolymerizate dispersion used in Example 4, 2.5 parts parts of the dispersion containing a copolymerizate of different acrylic acid esters used in Example 4, and 21 parts of water, are intimately mixed with each other and the resulting dispersion is used as described in Example 1 for the production of a top layer on the color layer obtained in step (a) of this example.

The resulting transcriptive paper possesses good qualities similar to those of the paper produced in Example 1.

What is claimed is:

1. A process for the manufacture of transcriptive materials producing a positive copy of writing on an underlying surface without the use of carbon paper or the like, which process comprises:

(a) coating at least a portion of one surface of a flexible sheet carrier with a mixture of a colored pigment and a high-molecular weight binding agent free from waxy, oily and fatty components by applying said mixture in a volatile solvent; and

(b) drying said color layer to such hardness that it does not give 013? color transferable directly to a writing sheet placed thereunder when the carrier of the color layer is written upon with pressure on its uncoated surface; and

(c) applying to the dried color layer an aqueous dispersion containing as essential dispersed matter 4.5 to 14% by weight of aliphatic saturated polycarboxylic acid of a molecular weight ranging from 1,000 to 20,000 and an acid number in the range of to 150, which acid comprises a main chain of carbon atoms the terminal groups of which are free from carboxyl groups, and the carboxyl groups are bonded to said main chain as branches, said acids being the product of the oxidation of branched polyethylene or polypropylene or the copolymerization product of mixtures of ethylene or propylene with unsaturated monoor di-carboxylic acids; and

(d) drying the top layer formed by said dispersion at a temperature below the fusion point of said polycarboxylic acid.

2. A process as described in claim 1, wherein carboxyl groups of the said carboxylic acid are bonded to aliphatic sides chains of from 1 to 4 carbon atoms which are in turn linked to said main chain of carbon atoms.

3. A process as described in claim 1, wherein carboxyl groups of the said polycarboxylic acid are linked to said main chain via methylene branch groups.

4. A process as described in claim 1, wherein carboxyl groups of the said polycarboxylic acid are linked to said main chain via ethylene branch groups.

5. A process as described in claim 1, wherein the said polycarboxylic acid is of a molecular weight of 1,000 to 4,000 and has an acid number in the range of 100 to 150.

6. A process as described in claim 1, wherein the polycarboxylic acid is of a molecular weight of 15,000 to 20,000 and has an acid number in the range of 10 to 30.

7. A process as described in claim 1, wherein the said polycarboxylic acid contains such portion of the carboxyl groups thereof in esterified form that the saponification number of the said polycarboxylic acid is in the range of 30 to 70 and the acid number is in the range of 10 to 140.

8. A process as described in claim 7, wherein the said polycarboxylic acid contains free carboxylic acid groups as well as esterified carboxylic acid groups, and wherein said esterified carboxylic acid groups are esterified with an aliphatic alcohol of from 1 to 20 carbon atoms.

9. A process as described in claim 7, wherein from about 1% to of the total number of carboxyl groups in the molecule of said polycarboxylic acid have been esterified with alkanol of from 1 to 20 carbon atoms.

10. A process as described in claim 7, wherein from about 1% to 80% of the total number of carboxyl groups in the molecule of said polycarboxylic acid have been esterified with aliphatic ether alcohol of from 2 to 21 carbon atoms and of from 1 to 10 oxygen atoms, the alcohol moiety of said esterified carboxyl groups bearing a terminal hydroxyl group.

11. A process as described in claim 7, wherein from about 1% to 80% of the total number of carboxyl groups in the molecule of said polycarboxylic acid have been esterified with aliphatic ether alcohol of from 2 to 21 carbon atoms and of from 1 to 10 oxygen atoms, the alcohol moiety of said esterified carboxy groups bearing a terminal hydroxyl group, said polycarboxylic acid having a saponification number in the range of from 50 to 70 and an acid number in the range of from 15 to 45.

12. A process as described in claim 1, wherein the said polycarboxylic acid is mixed in said aqueous dispersion thereof with a .water-dispersible polymerizate selected from the group consisting of vinyl homopolymerizate, vinyl chloride-acrylic acid copolymerizate, vinyl chlorideacrylic acid-vinyl ester copolymerizate, acrylic acid amide polymerizate, methacrylic acid polymerizate, methacrylic acid ester polymerizate, montan wax containing carboxyl groups and montan wax containing esterified carboxyl groups.

13. A process as described in claim 12, wherein the esterified products mentioned therein contain lower alkyl groups as the esterifying groups.

14. A process as described in claim 12, wherein said polycarboxylic acid is mixed in said aqueous dispersion thereof with polyacrylic acid ester and with alkanol of from 1 to 10 carbon atoms.

15. A process as described in claim 12, wherein the said polycarboxylic acid is mixed in said aqueous dispersion thereof with vinyl chloride-acrylic acid copolymerizate.

16. A process as described in claim 12, wherein the said polycarboxylic acid is mixed in said aqueous dispersion with acrylic acid lower alkyl ester polymerizate and vinyl chloride-acrylic acid copolymerizate.

17. A process as described in claim 12, wherein the said polycarboxylic acid is mixed in said aqueous dispersion thereof with montan wax ester.

(18. A process as described in claim 12, wherein the said polycarboxylic acid is mixed in said aqueous dispersion thereof with polyacrylic acid ester and montan wax ester.

19. A process as described in claim 12, wherein the said polycarboxylic acid is mixed in said aqueous dispersion thereof with vinyl chloride-acrylic acid copolymerizate and montan wax ester.

20. A process as described in claim 12, wherein the said polycarboxylic acid is mixed in said aqueous dispersion thereof with polyacrylic acid ester, vinyl chlorideacrylic acid copolymerizate and montan wax ester.

21. A process as described in claim 1, wherein said drying of said top layer is carried out in an air stream having a temperature of not more than 55 C.

22. A process as described in claim -1, wherein said drying of said top layer is carried out by infrared heating of said carrier at a temperature of not more than 55 C.

23. A transcriptive material producing a positive copy of the writing of an underlying surface without the use of carbon paper or the like, which material comprises a flexible sheet carrier at least a portion of one surface of which bears a color layer consisting essentially of a mixture of a colored pigment and a high-molecularweight binding agent free from waxy, oily and fatty components, and a top layer covering said color layer and consisting essentially of a deposit obtained from an aqueous dispersion of 4.5 to 14% by 'weight of aliphatic saturated polycarboxylic acid of a medium molecular weight ranging from 1,000 to 20,000 and an acid number of 10 to 150, which acid comprises a main chain of carbon atoms the terminal groups of which are free from carboxyl groups, and the carboxyl groups are bonded to said main chain as aliphatic saturated branches of from 1 to 4 carbon atoms, said acids being the product of the oxidation of branched polyethylene or polypropylene or the copolymerization product of mixtures of ethylene or propylene with unsaturated monoor di-carboxylic acids.

24. A transcriptive material as described in claim 23, wherein the said polycarboxylic acid contains such portion of the carboxyl groups thereof in esterified form that the saponification number of the said polycarboxylic acid is in the range of 30 to and the acid number is in the range of 10 to 140.

FOREIGN PATENTS 12/1962 France.

OTHER REFERENCES Worth: Chemistry and Technology of Waxes, 2 Ed., 1956, Reinhold Pub., N.Y. pp., 365-367.

MURRAY KATZ, Primary Examiner 

